Triamine/aspartate curative and coatings comprising the same

ABSTRACT

The reaction product of a triamine and a dialkyl maleate and/or dialkyl fumarate, wherein the reaction product has a viscosity of less than 2000 cPs is disclosed. Polyurea coatings comprising this reaction product are also disclosed, as are substrates coated with the same.

FIELD OF THE INVENTION

The present invention is directed to the reaction product of a triamineand a dialkyl maleate and/or dialkyl fumarate, wherein the reactionproduct has a viscosity of less than 2000 centiPoise (cPs).

The present invention is further directed to a polyurea comprising sucha reaction product, and to a substrate coated therewith.

BACKGROUND OF THE INVENTION

Coating compositions comprising polyureas are used in a wide variety ofindustries such as automotive, watercraft, aircraft, industrial,construction, military, recreational equipment including sportsequipment and the like. In these industries, considerable efforts havebeen made to develop coating compositions that will impart the desiredproperties to the substrate or article being coated. For example,coatings are used to protect against damage due to corrosion, abrasion,impact, chemicals, ultraviolet light, flame, heat, and/or otherenvironmental exposure. In addition to any of these functionalproperties, coatings can also be used for decorative purposes.

Polyureas are generally formed by reacting amines and isocyanates. Theuse of amines such as polyamines as crosslinkers or “curatives” is wellknown. For example, amines are known to crosslink with isocyanates toform urea compounds. Amines are also known to be reactive with, andtherefore used with, activated unsaturated groups, epoxy groups,aromatic activated aldehyde groups, cyclic carbonate groups, and acidand anhydride and ester groups. Polyamine crosslinkers with primaryamino groups can be quite reactive with some of these functionalitiesunder ambient or low temperature conditions (i.e. less than 100° C.).This high reactivity can result in too short a potlife or otherdifficulties in application, such as in high pressure impingementspraying. Certain aliphatic secondary amines, however, are not reactiveenough with these various functionalities. It is therefore desired toprovide amine curatives that are sufficiently reactive, but that providean adequate potlife. There is a further desire to provide such aminecuratives that impart the desired characteristics to the finalcomposition in which they are used.

SUMMARY OF THE INVENTION

The present invention is directed to the triamine/aspartate reactionproduct of a triamine and a dialkyl maleate and/or a dialkyl fumarate,wherein the triamine/aspartate reaction product has a viscosity of lessthan 2000 cPs.

The present invention is further directed to a coating compositioncomprising polyurea formed from a reaction mixture comprising isocyanateand a triamine/aspartate reaction product of a triamine and a dialkylmaleate and/or dialkyl fumarate, wherein the triamine/aspartate reactionproduct has a viscosity of less than 2000 cPs.

The present invention is further directed to a substrate coated at leastin part with a multilayer coating composite, comprising one or more ofan electrocoat layer, a base coat layer, and a clearcoat layer; and acoating comprising a polyurea formed from a reaction mixture comprisingisocyanate and a triamine/aspartate reaction product of a triamine and adialkyl maleate and/or dialkyl fumarate, wherein the triamine/aspartatereaction product has a viscosity of less than 2000 cPs.

DETAILED DESCRIPTION OF THE INVENTION

The present invention is directed to the triamine/aspartate reactionproduct of a triamine and a dialkyl maleate and/or a dialkyl fumarate,wherein the triamine/aspartate reaction product has a viscosity of lessthan 2000 cPs. The reaction product is sometimes referred to herein asthe “triamine/aspartate reaction product”, or simply as the“triamine/aspartate” or the “reaction product”, or like terms; thatreaction product may be referred to herein as a “curative” because itwill react or cure with an isocyanate to form a polyurea.

Any suitable triamine can be used according to the present invention. Atriamine will be understood as typically having the general formula

wherein each n is the same or different and is any integer. Dialkylenetriamines are particularly suitable, especially dipropylene triaminewhere n=3. Bis(hexamethylene)triamine, where n=6, is also particularlysuitable.

It will be appreciated by those skilled in the art that certaintriamines may contribute to the viscosity of the reaction product. Forexample, cycloaliphatic amines may make the resulting reaction producthighly viscous. Accordingly, in certain embodiments of the presentinvention, the use of cycloaliphatic amines, including cycloaliphatictriamines, is specifically excluded. Viscosity can be measured, forexample, using a Brookfield viscometer or using charts that convertviscosities of Newtonian fluids from Gardner Bubble viscosities tocentiPoise. It has been discovered that a viscosity of less than 2000cPs provides ease of handling, that is, pumping, but is also optimal forapplication. Viscosity influences the mixing efficiency of thetriamine/aspartate reaction product and polyisocyanate components informing the polyureas described herein.

Any dialkyl maleate and/or dialkyl fumarate can be used according to thepresent invention. Examples of suitable dialkyl maleates and fumaratesinclude but are not limited to esters of maleic acid and fumaric acidwith monoalcohols such as dimethyl, diethyl, di-n-propyl, di-isopropyl,di-n-butyl, di-sec-butyl, di-tert-butyl, di-isobutyl, di-penyl,di-t-amyl, di-hexyl, cyclohexyl and di-2-ethylhexyl maleates or thecorresponding fumarates. In certain embodiments, dialkyl maleates ordialkyl fumarates with two different alkyl groups, and/or mixtures ofdialkyl maleates and dialkyl fumarates can be used. The alkyl groups ofdialkyl maleate and/or dialkyl fumarate may comprise additionalfunctional groups such as hydroxyl groups, such as the reaction productof maleic anhydride, an alcohol, and an epoxy, the reaction product ofmaleic acid or fumaric acid with an alcohol and an epoxy, or thereaction product of maleic acid or fumaric acid with an epoxy. Suitablealcohols include but are not limited to methanol, ethanol, propanol,isopropanol, butanol, isobutanol, sec-butanol, tert-butanol, variousisomeric pentanols, various isomeric hexanols, cyclohexanol,2-ethylhexanol, and the like. Suitable epoxies include but are notlimited to ethylene oxide, propylene oxide, 1,2-epoxybutane, andglycidyl neodecanoate (an example of which is CARDURA E10P, HexionSpeciality Chemicals, Inc.).

The triamine and dialkyl maleate and/or dialkyl fumarate can be reactedin any ratio to give the desired reaction product. In certainembodiments, the equivalent ratio of amine to dialkyl maleate/dialkylfumarate is substantially stoichiometric. In other embodiments, anexcess of amine can be used to insure the conversion of the dialkylmaleate/dialkyl fumarate groups, or to leave some unreacted aminefunctionality. In certain embodiments, the reaction product issubstantially free of unreacted primary amino groups. Minimizing theamount of residual primary amine in the triamine/aspartate slows itsrate of reaction with isocyanate; thus, the ratio of amine to dialkylmaleate/dialkyl fumarate can be varied depending on the level ofreactivity desired in the resulting triamine/aspartate. Accordingly, incertain other embodiments, an excess of amine to dialkyl maleate/dialkylfumarate can be used to alter the cure speed in the subsequent polyureacomposition. In a particular embodiment, the equivalent ratio of amineto dialkyl maleate/dialkyl fumarate is 3:2; in this embodiment, theresulting secondary amines will have differing reactivities. That is,the nitrogen of these secondary amines, known as aspartates, is in asterically crowded environment. In addition, the ester portion of thestructure may provide inductive effects. Both of these features act toslow down the reaction of the secondary amines of the reaction productand the isocyanate group in the formation of the polyurea.

The triamine/aspartate reaction product of the present invention can beformed, for example, in the manner described in the examples, or anyother suitable manner. For example, the dialkyl maleate and/or dialkylfumarate can be added to the triamine at 20-75° C. in a manner so thatthe primary amine undergoes Michael addition with the dialkyl maleateand/or dialkyl fumarate and the reaction temperature is controlled. Thereaction mixture can then be heated to a temperature of up to 75° C. tocomplete the reaction. The reaction and consumption of maleate orfumarate double bonds can be monitored by several analytical methods.These include infrared (IR), proton and carbon-13 nuclear magneticresonance (NMR) spectroscopy. When a dialkyl maleate is used, infraredspectroscopy can be used to monitor the disappearance of thecarbon-carbon double bond stretch at 1645-1650 cm⁻¹ over time until thereaction is complete or no further change occurs. When proton NMRspectroscopy is used the disappearance of the vinyl hydrogen peaks at6.25 ppm is monitored. When carbon-13 NMR is used the disappearance ofthe carbonyl carbon peak at 165 ppm is monitored. Any suitable ratio oftriamine to dialkyl maleate and/or dialkyl fumarate can be used, such asthose described above.

The present invention is further directed to a coating comprising apolyurea formed from a reaction mixture comprising isocyanate and atriamine/aspartate reaction product of a triamine and a dialkyl maleateand/or a dialkyl fumarate. In certain embodiments, the ratio ofequivalents of isocyanate groups to equivalents of amine groups isgreater than 1 and the isocyanate and the triamine/aspartate reactionproduct can be applied to the substrate at a volume mixing ratio of 1:1.

As used herein, the term “isocyanate” includes unblocked compoundscapable of forming a covalent bond with a reactive group such as ahydroxyl or amine functional group. Thus, isocyanate can refer to “freeisocyanate”, which will be understood to those skilled in the art. Inalternate non-limiting embodiments, the isocyanate of the presentinvention can be monofunctional containing one isocyanate functionalgroup (NCO) or the isocyanate used in the present invention can bepolyfunctional containing two or more isocyanate functional groups(NCOs).

Suitable isocyanates for use in the present invention are numerous andcan vary widely. Such isocyanates can include those that are known inthe art. Non-limiting examples of suitable isocyanates can includemonomeric and/or polymeric isocyanates. The polyisocyanates can beselected from monomers, prepolymers, oligomers, or blends thereof. In anembodiment, the polyisocyanate can be C₂-C₂₀ linear, branched, cyclic,aromatic, or blends thereof.

Suitable isocyanates for use in the present invention may include butare not limited to isophorone diisocyanate (IPDI), which is3,3,5-trimethyl-5-isocyanato-methyl-cyclohexyl isocyanate; hydrogenatedmaterials such as cyclohexylene diisocyanate, 4,4′-methylenedicyclohexyldiisocyanate (H₁₂MDI); mixed aralkyl diisocyanates such astetramethylxylyl diisocyanates, OCN—C(CH₃)₂—C₆H₄C(CH₃)₂—NCO;polymethylene isocyanates such as 1,4-tetramethylene diisocyanate,1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate (HMDI),1,7-heptamethylene diisocyanate, 2,2,4- and 2,4,4-trimethylhexamethylenediisocyanate, 1,10-decamethylene diisocyanate and2-methyl-1,5-pentamethylene diisocyanate; and mixtures thereof.

Non-limiting examples of aromatic isocyanates for use in the presentinvention may include but are not limited to phenylene diisocyanate,toluene diisocyanate (TDI), xylene diisocyanate, 1,5-naphthalenediisocyanate, chlorophenylene 2,4-diisocyanate, bitoluene diisocyanate,dianisidine diisocyanate, tolidine diisocyanate, alkylated benzenediisocyanates, methylene-interrupted aromatic diisocyanates such asmethylenediphenyl diisocyanate, 4,4′-isomer (MDI) including alkylatedanalogs such as 3,3′-dimethyl-4,4′-diphenylmethane diisocyanate,polymeric methylenediphenyl diisocyanate and mixtures thereof.

In a non-limiting embodiment, polyisocyanate monomer may be used. It isbelieved that the use of a polyisocyanate monomer (i.e., residual-freemonomer from the preparation of prepolymer) may decrease the viscosityof the polyurea composition thereby improving its flowability, and mayprovide improved adhesion of the polyurea coating to a previouslyapplied coating and/or to an uncoated substrate. For example, thecoatings that have been previously applied to a substrate can comprisefunctional groups (e.g. hydroxy groups) that are reactive withisocyanates, thereby enhancing adhesion of this coating to the polyureacomposition of the present invention applied over this coating. A lowerviscosity polyurea composition may also remain in a “flowable” state fora longer period of time as compared to a comparable composition having ahigher viscosity. In alternate embodiments of the present invention, atleast 1 percent by weight, or at least 2 percent by weight, or at least4 percent by weight of the isocyanate component comprises at least onepolyisocyanate monomer.

In a further embodiment of the invention, the isocyanate can includeoligomeric polyisocyanates including but not limited to dimers, such asthe uretdione of 1,6-hexamethylene diisocyanate, trimers, such as thebiuret and isocyanurate of 1,6-hexanediisocyanate and the isocyanurateof isophorone diisocyanate, and polymeric oligomers. Modifiedpolyisocyanates can also be used, including but not limited tocarbodiimides and uretidiones, and mixtures thereof. Suitable materialsinclude, without limitation, those available under the designationDESMODUR from Bayer Corporation of Pittsburgh, Pa. and include DESMODURN 3200, DESMODUR N 3300, DESMODUR N 3400, DESMODUR XP 2410, and DESMODURXP 2580.

As used herein, “isocyanate prepolymer” means polyisocyanate that ispre-reacted with polyamine or another isocyanate reactive group such aspolyol. Suitable polyisocyanates include those previously disclosedherein. Suitable polyamines are numerous and may be selected from a widevariety known in the art. Examples of suitable polyamines include butare not limited to primary and secondary amines, and mixtures thereof,such as any of those listed herein. Amine terminated polyureas may alsobe used. Amines comprising tertiary amine functionality can be usedprovided that the amine further comprises at least two primary and/orsecondary amino groups. Suitable polyols are numerous and may beselected from a wide variety known in the art. Examples of suitablepolyols include but are not limited to polyether polyols, polyesterpolyols, polyurea polyols (e.g. the Michael reaction product of an aminofunction polyurea with a hydroxyl functional (meth)acrylate),polycaprolactone polyols, polycarbonate polyols, polyurethane polyols,poly vinyl alcohols, addition polymers of unsaturated monomers withpendant hydroxyl groups such as those containing hydroxy functional(meth)acrylates, allyl alcohols and mixtures thereof.

In certain embodiments, the isocyanate includes an isocyanate prepolymerand in other embodiments the isocyanate includes an isocyanateprepolymer and one or more additional isocyanates, such as one or moreof the polyisocyanates described above.

As noted above, the polyurea of the present invention is formed from areaction mixture comprising isocyanate and the triamine/aspartatereaction product described above. The present polyurea compositions maycomprise more than one triamine/aspartate reaction product as describedherein or one or more other amine curatives in addition to thetriamine/aspartate reaction product(s). For example, the presentpolyurea compositions may comprise one or more amines that are thereaction product of an amine, a (meth)acrylate and a dialkyl maleateand/or dialkyl fumarate, such as those described in the U.S. patentapplication entitled: “(Meth)Acrylate/Aspartate Amine Curatives andCoatings and Articles Comprising the Same” filed on even date herewithand hereby incorporated by reference; one or more amines that are thereaction product of a polyamine, a poly(meth)acrylate and amono(meth)acrylate or monoamine, such as those described in the U.S.patent application entitled: “Polyurea Coating Comprising anAmine(Meth)Acrylate Oligomeric Reaction Product” filed on even dateherewith and hereby incorporated by reference; one or more amines thatare the reaction product of a polyamine and a mono(meth)acrylate, suchas those described in the U.S. patent application entitled: “PolyureaCoating Comprising a Polyamine/Mono(Meth)Acrylate Reaction Product”filed on even date herewith and hereby incorporated by reference; and/orone or more amines that are the reaction product of a monoamine and apoly(meth)acrylate, such as those described in the U.S. patentapplication entitled: “Substrates Coated with a Polyurea Comprising a(Meth)acrylated Amine Reaction Product” filed on even date herewith andhereby incorporated by reference.

The polyurea coating comprising the present triamine/aspartate curativeand an isocyanate can additionally include other amines including butnot limited to any monoamines, polyamines or combinations thereof knownin the art. Suitable primary polyamines include, but are not limited to,but not limited to, ethylene diamine, 1,2-diaminopropane,1,4-diaminobutane, 1,3-diaminopentane (DYTEK EP, Invista),1,6-diaminohexane, 2-methyl-1,5-pentane diamine (DYTEK A, Invista),2,5-diamino-2,5-dimethylhexane, 2,2,4- and/or2,4,4-trimethyl-1,6-diamino-hexane, 1,11-diaminoundecane,1,12-diaminododecane, 1,3- and/or 1,4-cyclohexane diamine,1-amino-3,3,5-trimethyl-5-aminomethyl-cyclohexane, 2,4- and/or2,6-hexahydrotoluylene diamine, 2,4′-diaminodicyclohexyl methane,4,4′-diaminodicyclohexyl methane (PACM-20, Air Products) and3,3′-dialkyl-4,4′-diaminodicyclohexyl methanes (such as3,3′-dimethyl-4,4′-diaminodicyclohexyl methane (DIMETHYL DICYKAN orLAROMIN C260, BASF; ANCAMINE 2049, Air Products) and3,3′-diethyl-4,4′-diaminodicyclohexyl methane), 2,4- and/or2,6-diaminotoluene and 2,4′- and/or 4,4′-diaminodiphenyl methane. Otheramines include secondary cycloaliphatic diamines such as JEFFLINK 754(Huntsman Corporation, Houston, Tex.) and CLEARLINK 1000 (Dorf-KetalChemicals, LLC), aspartic ester functional amines, such as thoseavailable under the name DESMOPHEN such as DESMOPHEN NH1220, DESMOPHENNH 1420, and DESMOPHEN NH 1520 (Bayer Corporation).Polyoxyalkyleneamines are also suitable. Polyoxyalkyleneamines comprisetwo of more primary or secondary amino groups attached to a backbone,derived, for example, from propylene oxide, ethylene oxide, butyleneoxide or a mixture thereof. Examples of such amines include thoseavailable under the designation JEFFAMINE, such as, without limitation,JEFFAMINE D-230, D-400, D-2000, HK-511, ED-600, ED-900, ED-2003, T-403,T-3000, T-5000, SD-231, SD-401, SD-2001, and ST-404 (HuntsmanCorporation). Such amines have an approximate molecular weight rangingfrom 200 to 7500. When more than one triamine/aspartate reaction productis used, the triamine(s) and dialkyl maleate(s) and/or dialkylfumarate(s) in each reaction product can be the same or different.

Other suitable secondary amines that can be included in the presentcomposition are reaction products of materials comprising primary aminefunctionality with acrylonitrile. Suitable amines include any polyaminelisted herein comprising primary amino functionality. One example ofsuch a material is the adduct of 4,4′-diaminodicyclohexylmethane andacrylonitrile. An example of a commercially available material is theadduct of isophorone diamine and acrylonitrile sold under thedesignation POLYCLEAR 136, (Hansen Group LLC).

Other amines that can be used are adducts of primary polyamines withmono or polyepoxies; an example of such a material is the adduct ofisophorone diamine with Cardura E10P (available from Hexion SpecialityChemicals, Inc). In certain embodiments, the amine component of thepolyurea, and/or the polyurea itself, are substantially free of primaryamine functionality (unreacted primary amino groups). “Substantiallyfree of primary amine functionality” and like terms means thattheoretically there is no primary amine functionality but there maybesome primary amine functionality present that is purely incidental, i.e.impurities in amines that are otherwise secondary amine functionaland/or trace primary amine functionality that did not react.

In an embodiment, the coating compositions of the present invention mayinclude a blend of polyurea and polyurethane. As used herein, therefore,“polyurea” includes both polyurea and blends of polyurea andpolyurethane. It will be appreciated by those skilled in the art thatpolyurethane can be formed as a by-product in the reactions of thepresent invention. In alternate embodiments, the polyurethane can beformed in-situ and/or it can be added to the reaction mixture; anon-limiting example is an NCO functional prepolymer formed by reactionof a polyol and a polyisocyanate as disclosed herein. A non-limitingexample of polyurethane formed in-situ may include the reaction productof polyisocyanate and hydroxyl-functional material. Non-limitingexamples of suitable polyisocyanates may include those described herein.Non-limiting examples of suitable hydroxyl-functional material mayinclude polyol such as those described herein. Another example ofpolyurethane formed in-situ may include the reaction product of hydroxylfunctional prepolymer and isocyanate-functional material. Suitableexamples of these reactants may include those described herein.

The polyurea coating compositions of the present invention may beformulated and applied using various techniques known in the art.Accordingly, the present invention is further directed to methods forcoating a substrate comprising applying to at least a portion of thesubstrate any of the coating compositions described herein. In anembodiment, conventional spraying techniques may be used. In thisembodiment, the isocyanate and amine may be combined such that the ratioof equivalents of isocyanate groups to equivalents of amine groups isgreater than 1 and the isocyanate and amine can be applied to asubstrate at a volume mixing ratio of 1:1; the reaction mixture may beapplied to an uncoated or coated substrate to form a first coating onthe uncoated substrate or a subsequent coating on the coated substrate.When determining the ratio of equivalents of isocyanate groups toequivalents of amine group, the total reactive amine groups are takeninto consideration; that is the amine groups from the triamine/aspartatecurative as well as any other amine used in the coating.

It will be appreciated that the present compositions can be twocomponent or “2K” compositions, wherein the isocyanate-containingcomponent and the amine-containing component are kept separate untiljust prior to application. Such compositions will be understood ascuring under ambient conditions, although a heated forced air or a heatcure can be applied to accelerate final cure or to enhance coatingproperties such as adhesion. In an embodiment, the sprayable coatingcomposition may be prepared using a two-component mixing device. In thisembodiment, isocyanate and amine are added to a high pressureimpingement mixing device. The isocyanate is added to the “A-side” andamine is added to the “B-side”. The A- and B-side streams are impingedupon each other and immediately sprayed onto at least a portion of anuncoated or coated substrate. The isocyanate and the amine react toproduce a coating composition that is cured upon application to theuncoated or coated substrate. The A- and/or B-side can also be heatedprior to application, such as to a temperature of 140° F. Heating maypromote a better viscosity match between the two components and thusbetter mixing, but is not necessary for the curing reaction to occur.

In a non-limiting embodiment, a commercially available mixing deviceavailable commercially under the designation GUSMER VR-H-3000proportioner fitted with a GUSMER Model GX-7 spray gun may be used. Inthis device, pressurized streams of the A- and B-side components aredelivered from two separate chambers and are impacted or impinged uponeach other at high velocity to mix the two components and form a coatingcomposition, which may be applied to an uncoated or coated substrateusing the spray gun. The mixing forces experienced by the componentstreams may be depend upon the volume of each stream entering the mixingchamber per unit time and the pressure at which the component streamsare delivered. A 1:1 volume ratio of the isocyanate and amine per unittime may equalize these forces.

Another suitable application device known in the industry includes a“static mix tube” applicator. In this device, the isocyanate and amineare each stored in a separate chamber. As pressure is applied, each ofthe components is brought into a mixing tube in a 1:1 ratio by volume.Mixing of the components is effected by way of a torturous or cork screwpathway within the tube. The exit end of the tube may have atomizationcapability useful in spray application of the reaction mixture.Alternatively, the fluid reaction mixture may be applied to a substrateas a bead. A static mix tube applicator is commercially available fromCammda Corporation.

The polyurea coating compositions of the present invention may beapplied to a wide variety of substrates. Accordingly, the presentinvention is further directed to a substrate coated with any of thecompositions described herein. Non-limiting examples of suitablesubstrates can include but are not limited to metal, natural and/orsynthetic stone, ceramic, glass, brick, cement, concrete, cinderblock,wood and composites and laminates thereof; wallboard, drywall,sheetrock, cement board, plastic, paper, PVC, styrofoam, plasticcomposites, acrylic composites, ballistic composites, asphalt,fiberglass, soil, gravel and the like. “Metallic substrate(s)” includessubstrates comprising metal(s) and/or metal alloys, including but notlimited to aluminum, any form of steel such as cold rolled steel,electrogalvanized steel, hot dipped galvanized steel, titanium and thelike. Plastics can include but are not limited to TPO, SMC, TPU,polypropylene, polycarbonate, polyethylene, polyamides (Nylon). Thesubstrates can be primed metal and/or plastic; that is, an organic orinorganic layer is applied thereto. Further, the coating compositions ofthe present invention can be applied to said substrates to impart one ormore of a wide variety of properties such as but not limited tocorrosion resistance, abrasion resistance, impact damage, flame and/orheat resistance, chemical resistance, UV light resistance, structuralintegrity, ballistic mitigation, blast mitigation, sound dampening,decoration and the like. In non-limiting examples, the coatingcompositions of the present invention can be applied to at least aportion of a building component or an article of manufacture such as butnot limited to a vehicle. “Vehicle” includes but is not limited tocivilian, commercial, and military land-, water-, and air-vehicles, forexample, cars, trucks, boats, ships, submarines, airplanes, helicopters,humvees and tanks. The article of manufacture can be a buildingstructure. “Building component” and like terms includes but is notlimited to at least a portion of a structure including residential,commercial and military structures, for example, roofs, floors, supportbeams, walls and the like. As used herein, the term “substrate” mayrefer to a surface, either external or internal, on at least a portionof an article of manufacture, the article of manufacture itself, abuilding component and the like. In an embodiment, the substrate is atruck bed.

In an embodiment, the polyurea coating composition of the presentinvention may be applied to a carrier film. The carrier film can beselected from a wide variety of such materials known in the art.Non-limiting examples of suitable carrier films may include, but are notlimited to thermoplastic materials, thermosetting materials, metalfoils, cellulosic paper, synthetic papers, and mixtures thereof. As usedherein, the term “thermoplastic material” refers to any material that iscapable of softening or fusing when heated and of solidifying(hardening) again when cooled. Non-limiting examples of suitablethermoplastic materials may include polyolefins, polyurethanes,polyesters, polyamides, polyureas, acrylics, and mixtures thereof. Asused herein, the term “thermosetting material” refers to any materialthat becomes permanently rigid after being heated and/or cured.Non-limiting examples may include polyurethane polymers, polyesterpolymers, polyamide polymers, polyurea polymers, polycarbonate polymers,acrylic polymers, aminoplasts, isocyanates, epoxies, copolymers thereof,and mixtures thereof.

As noted above, in certain embodiments, the polyurea coatingcompositions of the present invention may be applied to a bare (e.g.,untreated, uncoated) substrate, a pretreated substrate and/or coatedsubstrate having at least one other coating. In a non-limitingembodiment, the coating compositions of the present invention may beapplied as part of a multi-layer coating composite. The first coatingapplied to a substrate may be selected from a variety of coatingcompositions known in the art for surface coating substrates.Non-limiting examples may include but are not limited toelectrodepositable film-forming compositions, primer compositions,pigmented or non-pigmented monocoat compositions, pigmented ornon-pigmented base coat compositions, transparent topcoat compositions,industrial coating compositions, and the like. In another non-limitingembodiment, the coating compositions of the present invention may beapplied as part of a multi-layer coating composite comprising apretreated substrate and coating layers such as but not limited toelectrocoat, primer, base coat, clear coat, and combinations thereof. Inan embodiment, the clear coat comprises silane functional groups eitherbefore or after crosslinking and cure.

Accordingly, certain embodiments of the present invention are directedto a substrate coated at least in part with a multilayer coatingcomposite, comprising at least one of an electrocoat layer, a base coatlayer, and a clearcoat layer, in addition to a polyurea layer formedfrom a reaction mixture comprising isocyanate and a triamine/aspartatereaction product of a triamine and a dialkyl maleate and/or dialkylfumarate. In certain embodiments, the multilayer coating compositecomprises at least two of an electrocoat layer, a base coat layer, and aclearcoat layer, in addition to the polyurea layer described above, andin yet other embodiments the multilayer coating composite comprises anelectrocoat layer, a basecoat layer, and a clearcoat layer, in additionto the polyurea layer described above. An electrocoat layer is onedeposited from an electrodepositable film-forming composition, typicallyused in a variety of industries for decorative and/or protectivepurposes. A base coat layer can be deposited from any pigmented ornon-pigmented base coat composition. Typically, a pigmented base coat isused in conjunction with a clearcoat. A clearcoat layer can be depositedfrom any clear coat composition. In an embodiment, the clear coatcomprises silane functional groups either before or after crosslinkingand cure. In another embodiment, the clearcoat has low surfacefunctionality after cure, such as carbamate melamine, hydroxyl melamine,2K urethane, and silane-containing clearcoats. Any number of additionalcoating and/or treatment layers can be used according to the presentinvention in conjunction with the electrocoat, base coat, clearcoatand/or polyurea layers according to the present invention, such aspre-treatment layers before the electrocoat layer, primer layers,additional electrocoat, base coat and/or clearcoat layers and the like.The substrate can be any suitable substrate, such as any of thosedescribed herein.

In a further embodiment, the polyurea coating compositions of thepresent invention can be used in a two-coat application resulting in atextured surface. A first coat is applied to an uncoated or coatedsubstrate to produce a smooth, substantially tack-free layer. The“Tack-Free Method” is used to determine if the layer is substantiallytack-free. The Tack-Free Method includes spraying the coatingcomposition in one coat onto a non-adhering plastic sheet to a thicknessof from 10 to 15 mil (254-381 microns). When spraying is complete, anoperator, using a loose fitting, disposable vinyl glove, such as onecommercially available as AMBIDEX Disposable Vinyl Glove by MarigoldIndustrial, Norcross Ga., gently touches the surface of the coating. Thecoating may be touched more than one time by using a differentfingertip. When the glove tip no longer sticks to, or must be pulledfrom, the surface of the layer, the layer is said to be substantiallytack-free. The time beginning from the completion of spraying until whenthe coating is substantially tack-free is said to be the tack-free time.In a non-limiting embodiment, the tack-free time and the cure time maybe controlled by balancing levels of various composition components suchas the ratio of primary amine to secondary amine.

A second coat may then be applied to the first coating layer as atexturizing layer or “dust coating”. The second coating layer can beapplied by increasing the distance between the application/mixing deviceand the coated substrate to form discrete droplets of the coatingcomposition prior to contacting the coated substrate thereby formingcontrolled non-uniformity in the surface of the second layer. Thesubstantially tack-free first layer of the coating is at least partiallyresistant to the second layer; i.e., at least partially resistant tocoalescence of the droplets of coating composition sprayed thereon asthe second layer or dust coating such that the droplets adhere to but donot coalesce with the previous layer(s) to create surface texture. Thefinal coating layer typically exhibits more surface texture than thefirst or previous coating layers. An overall thickness of the coatinglayers may range from 20 to 1000 mils, or from 40 to 150 mils, or from60 to 100 mils (1524-2540 microns), or from 500 to 750 mils. In anon-limiting embodiment, the first layer may be the majority of thetotal thickness and the dust coating may be from 15-50 mils (381-1270microns).

In various embodiments of the present invention, the “first” coatinglayer may comprise one, two, three or more layers; and the “second”coating layer may be one or more subsequent layers applied thereover.For example, four polyurea layers may be applied, with the fourth layerbeing the dust coating and each layer having a thickness of from 15 to25 mil (381-635 microns). It will be appreciated that these coatinglayers are relatively “thick”. The coating compositions of the presentinvention can also be applied as much thinner layers as well, such as0.1 to less the 15 mils, such as 0.1 to 10, 0.5 to 3 or 1 to 2 mils.Such layers can be used alone or in conjunction with other coatinglayers, such as any of those known in the art or otherwise describedherein. When applied at a sufficient thickness (e.g. 10 to 1000 mils,such as 100 to 200 mils, or 125 mils+/−10 mils), the present polyurealayer(s) can provide blast mitigation. “Blast mitigation” means, forexample, protection in the event of a close proximity blast orexplosion. This protection can include, for example, protection of astructure or portion of a structure, such as a building structure,vehicle, aircraft, ship/boat, shipping container and the like, fromcollapse and/or destruction, protection against flying debris and blastfragments, and the like.

In alternate embodiments, the coating layers may comprise the same ordifferent polyurea coating compositions. For example, the first layermay be a polyurea composition comprising aliphatic and/or aromatic aminecomponents and/or aliphatic and/or aromatic polyisocyanate and thesecond layer may comprise the same or different combination of aliphaticand/or aromatic amine components and/or aliphatic and/or aromaticpolyisocyanate. “Amine component” in this context means any amine usedin the present coatings. In a further embodiment, the outermost coatinglayer may comprise a coating composition that provides a desireddurability. The desired durability may depend upon the use of thecoating composition of the present invention and/or the substrate towhich it may be applied. In an embodiment, a combination of aliphaticand/or aromatic amine and/or polyisocyanate may be selected such thatthe composition of the outermost layer has substantial durability. Forexample, the outermost coating layer may have a durability of 1000 kJ to6000 kJ, or from 800 hours to 4000 hours, when tested using aWeatherometer (Atlas Material Testing Solutions) in accordance withmethod SAE J1960. In this embodiment, the first layer may be a polyureacomposition comprising polyisocyanate and amine, wherein at least one ofthe amine and/or polyisocyanate may comprise an aromatic moiety, and thesecond layer may be a polyurea composition comprising predominantlyaliphatic amine and aliphatic polyisocyanate, with little or noaromaticity.

The polyurea coating compositions of the present invention mayoptionally include materials standard in the art such as but not limitedto fillers, fiberglass, stabilizers, thickeners, fillers, adhesionpromoters, catalysts, colorants, antioxidants, UV absorbers, hinderedamine light stabilizers, rheology modifiers, flow additives, anti-staticagents and other performance or property modifiers that are well knownin the art of surface coatings, and mixtures thereof. For example, thepresent coatings can further comprise flame and/or heat resistantmaterial, such as any one or more of those disclosed in U.S. applicationSer. No. 11/591,312, hereby incorporated by reference in its entirety.Fillers can include clay and/or silica, and adhesion promoters caninclude amine functional materials, aminosilanes and the like; examplesof fillers and adhesion promoters are further described in U.S.Publication No. 2006/0046068, hereby incorporated by reference in itsentirety. These additives can be combined with the isocyanate, thetriamine/aspartate reaction product, or both. In certain embodiments,the coating may further comprise small amounts, of solvent and incertain embodiments the coating may be substantially solvent-free.“Substantially solvent-free” means that the coating may contain a smallamount of solvent, such as 5%, 2%, 1% or less.

As used herein, the term “colorant” means any substance that impartscolor and/or other opacity and/or other visual effect to thecomposition. The colorant can be added to the coating in any suitableform, such as discrete particles, dispersions, solutions and/or flakes.A single colorant or a mixture of two or more colorants can be used inthe coatings of the present invention.

Example colorants include pigments, dyes and tints, such as those usedin the paint industry and/or listed in the Dry Color ManufacturersAssociation (DCMA), as well as special effect compositions. A colorantmay include, for example, a finely divided solid powder that isinsoluble but wettable under the conditions of use. A colorant can beorganic or inorganic and can be agglomerated or non-agglomerated.Colorants can be incorporated into the coatings by grinding into thecoating by use of a grind vehicle, such as an acrylic grind vehicle, theuse of which will be familiar to one skilled in the art. The grindvehicle can also comprise the triamine/aspartate of the presentinvention either in total or in combination with any other amines andpolyols as described herein.

Example pigments and/or pigment compositions include, but are notlimited to, carbazole dioxazine crude pigment, azo, monoazo, disazo,naphthol AS, salt type (lakes), benzimidazolone, metal complex,isoindolinone, isoindoline and polycyclic phthalocyanine, quinacridone,perylene, perinone, diketopyrrolo pyrrole, thioindigo, anthraquinone,indanthrone, anthrapyrimidine, flavanthrone, pyranthrone, anthanthrone,dioxazine, triarylcarbonium, quinophthalone pigments, diketo pyrrolopyrrole red (“DPPBO red”), titanium dioxide, carbon black, carbon fiber,graphite, other conductive pigments and/or fillers and mixtures thereof.The terms “pigment” and “colored filler” can be used interchangeably.

Example dyes include, but are not limited to, those that are solventbased such as pthalo green or blue, iron oxide, bismuth vanadate,anthraquinone, perylene, aluminum and quinacridone.

Example tints include, but are not limited to, pigments dispersed inwater-based or water miscible carriers such as AQUA-CHEM 896commercially available from Degussa, Inc., CHARISMA COLORANTS andMAXITONER INDUSTRIAL COLORANTS commercially available from AccurateDispersions division of Eastman Chemical, Inc.

As noted above, the colorant can be in the form of a dispersionincluding, but not limited to, a nanoparticle dispersion. Nanoparticledispersions can include one or more highly dispersed nanoparticlecolorants and/or colorant particles that produce a desired visible colorand/or opacity and/or visual effect. Nanoparticle dispersions caninclude colorants such as pigments or dyes having a particle size ofless than 150 nm, such as less than 70 nm, or less than 30 nm.Nanoparticles can be produced by milling stock organic or inorganicpigments with grinding media having a particle size of less than 0.5 mm.Example nanoparticle dispersions and methods for making them areidentified in U.S. Pat. No. 6,875,800 B2, which is incorporated hereinby reference. Nanoparticle dispersions can also be produced bycrystallization, precipitation, gas phase condensation, and chemicalattrition (i.e., partial dissolution). In order to minimizere-agglomeration of nanoparticles within the coating, a dispersion ofresin-coated nanoparticles can be used. As used herein, a “dispersion ofresin-coated nanoparticles” refers to a continuous phase in which isdispersed discreet “composite microparticles” that comprise ananoparticle and a resin coating on the nanoparticle. Exampledispersions of resin-coated nanoparticles and methods for making themare identified in U.S. application Ser. No. 10/876,031 filed Jun. 24,2004, which is incorporated herein by reference, and U.S. ProvisionalApplication No. 60/482,167 filed Jun. 24, 2003, which is alsoincorporated herein by reference.

Example special effect compositions that may be used in the polyureacoating of the present invention include pigments and/or compositionsthat produce one or more appearance effects such as reflectance,pearlescence, metallic sheen, phosphorescence, fluorescence,photochromism, photosensitivity, thermochromism, goniochromism and/orcolor-change. Additional special effect compositions can provide otherperceptible properties, such as opacity or texture. In a non-limitingembodiment, special effect compositions can produce a color shift, suchthat the color of the coating changes when the coating is viewed atdifferent angles. Example color effect compositions are identified inU.S. Pat. No. 6,894,086, incorporated herein by reference. Additionalcolor effect compositions can include transparent coated mica and/orsynthetic mica, coated silica, coated alumina, a transparent liquidcrystal pigment, a liquid crystal coating, and/or any compositionwherein interference results from a refractive index differential withinthe material and not because of the refractive index differentialbetween the surface of the material and the air.

In certain non-limiting embodiments, a photosensitive composition and/orphotochromic composition, which reversibly alters its color when exposedto one or more light sources, can be used in the coating of the presentinvention. Photochromic and/or photosensitive compositions can beactivated by exposure to radiation of a specified wavelength. When thecomposition becomes excited, the molecular structure is changed and thealtered structure exhibits a new color that is different from theoriginal color of the composition. When the exposure to radiation isremoved, the photochromic and/or photosensitive composition can returnto a state of rest, in which the original color of the compositionreturns. In one non-limiting embodiment, the photochromic and/orphotosensitive composition can be colorless in a non-excited state andexhibit a color in an excited state. Full color-change can appear withinmilliseconds to several minutes, such as from 20 seconds to 60 seconds.Example photochromic and/or photosensitive compositions includephotochromic dyes.

In a non-limiting embodiment, the photosensitive composition and/orphotochromic composition can be associated with and/or at leastpartially bound to, such as by covalent bonding, a polymer and/orpolymeric materials of a polymerizable component. In contrast to somecoatings in which the photosensitive composition may migrate out of thecoating and crystallize into the substrate, the photosensitivecomposition and/or photochromic composition associated with and/or atleast partially bound to a polymer and/or polymerizable component inaccordance with a non-limiting embodiment of the present invention, haveminimal migration out of the coating. Example photosensitivecompositions and/or photochromic compositions and methods for makingthem are identified in U.S. application Ser. No. 10/892,919 filed Jul.16, 2004 and incorporated herein by reference.

In general, the colorant can be present in the coating composition inany amount sufficient to impart the desired property, visual and/orcolor effect. The colorant may comprise from 0.1 to 65 weight percent ofthe present compositions, such as from 3 to 40 weight percent or 5 to 35weight percent, with weight percent based on the total weight of thecompositions. In certain embodiments, the weight percent of pigment maybe 01. to 1.0 weight percent.

In another embodiment, the polyurea coating compositions of the presentinvention when applied to a substrate possesses color that matches thecolor of an associated substrate. As used herein, the term “matches” orlike terms when referring to color matching means that the color of thecoating composition of the present invention substantially correspondsto a desired color or the color of an associated substrate. Forinstance, when the substrate for the polyurea coating composition is aportion of a vehicle, such as a truck bed, the color of the coatingsubstantially matches that of the associated vehicle body. This can bevisually observed, or confirmed using spectroscopy equipment.

The coatings of the present invention may be part of a multi-layercoating composite comprising a substrate with various coating layerssuch as a pretreatment layer, electrocoat, primer, base coat and clearcoat. At least one of the base coat and clear coat may contain pigmentand/or the clear coat may contain an adhesion promoter and any of thesecoatings can be the coatings described herein. It is believed that theaddition of adhesion promoter to the clear coat, or to its surface, mayimprove the adhesion between the clear coat and the coating compositionapplied thereover, although the inventors do not wish to be bound by anymechanism. In this embodiment, the coating composition of the presentinvention may be the reaction product of isocyanate and thetriamine/aspartate with a pigment additive. The coating composition ofthe present invention containing pigment may be applied to at least aportion of the article or structure. The color of the coated article orstructure may match the color of an associated substrate. An “associatedsubstrate” may refer to a substrate that comprises the article orstructure but is not coated with the coating composition of the presentinvention or a substrate that is attached, connected or in closeproximity to the article or structure, but is not coated with thecoating composition of the present invention.

As used herein, unless otherwise expressly specified, all numbers suchas those expressing values, ranges, amounts or percentages may be readas if prefaced by the word “about”, even if the term does not expresslyappear. Any numerical range recited herein is intended to include allsub-ranges subsumed therein. Plural encompasses singular and vice versa.For example, while the invention has been described herein including theclaims in terms of “a” triamine, “a” dialkyl maleate and/or dialkylfumarate, “a” triamine/aspartate reaction product, “a” polyurea, “a”substrate and the like, mixtures of all of such things can be used.Also, as used herein, the term “polymer” is meant to refer toprepolymers, oligomers and both homopolymers and copolymers; the prefix“poly” refers to two or more.

EXAMPLES

The following examples are intended to illustrate the invention, andshould not be construed as limiting the invention in any way. As will beappreciated by those skilled in the art MW refers to average molecularweight, M_(w) refers to weight average molecular weight and M_(n) refersto number average molecular weight.

Example A

An aspartate modified amine curative with a secondary non-aspartateamino group was prepared from the following ingredients:

Ingredient Wt in g Charge 1 Dipropylene triamine 2292.52,6-di-tert-butyl p-cresol 10.5 Charge 2 Diethyl maleate 5779.2

Charge 1 was added to a suitable flask equipped with an overheadstirrer, thermocouple, condenser, and N₂ inlet. The charge was placedunder an N₂ blanket. Beginning at a temperature of 22° C., Charge 2 wasadded to the flask over a period of 6 hours. An exotherm was observedduring the addition. A maximum temperature of 49° C. was observed duringthe addition of this charge. At temperature of 48° C. (3.75 hours intothe charge) cooling was applied to the reactor in the form of a streamof air. At a temperature of 49° C. (4.5 hours into the charge) an icebath was applied to the reactor. At the completion of the charge, thetemperature of the reaction mixture was 41° C. The reaction mixture washeated to a temperature of 50° C. with an external heat source and heldat this temperature for 3.6 hours. Inspection of the infrared spectrumof the reaction mixture indicated consumption of diethyl maleate(disappearance of peak at 1646 cm⁻¹). The resulting material was foundto have measured solids content (110° C., 1 hr) of 97.4 percent, aviscosity of E on the Gardner-Holt scale (approximately 125 cPs), adensity of 8.93 lb/gal, a total amine content of 6.303 meq/g, a residualprimary amine content of 0.298 meq/g, a secondary amine content of 6.011meq/g, a tertiary amine content of 0.044 meq/g, and a M_(w) of 248 and aM_(n) of 178 as determined by gel permeation chromatography vs. apolystyrene standard.

Example B

An aspartate modified amine curative with a secondary non-aspartateamino group was prepared from the following ingredients:

Ingredient Wt in g Charge 1 Bishexamethylene triamine 172.5 Charge 2Diethyl maleate 264.1

Charge 1 was added to a suitable flask equipped with an overheadstirrer, thermocouple, condenser, and N₂ inlet. The charge was placedunder an N₂ blanket. Beginning at a temperature of 60° C., Charge 2 wasadded to the flask over a period of 4.5 hours. A slight exotherm wasobserved during the addition. A maximum temperature of 67° C. wasobserved during the addition of this charge. At the completion of thecharge, the temperature of the reaction mixture was 61° C. The reactionmixture was heated to a temperature of 70° C. with an external heatsource and held at this temperature for 2.75 hours. Inspection of theinfrared spectrum of the reaction mixture indicated consumption ofdiethyl maleate (disappearance of peak at 1646 cm-1). The resultingmaterial was found to have measured solids content (110° C., 1 hr) of98.3 percent, a viscosity of F+ on the Gardner-Holt scale (approximately146 cPs), a density of 8.55 lb/gal, a total amine content of 5.17 meq/g,a residual primary amine content of 0.077 meq/g, a secondary aminecontent of 5.032 meq/g, a tertiary amine content of 0.066 meq/g, and aM_(w) of 547 and a M_(n) of 445 as determined by gel permeationchromatography vs. a polystyrene standard.

Example C

An amine/acrylate curative was prepared from the following ingredients:

Ingredient Wt in g Charge 1 2-ethylhexylamine 387.8 Charge 2Trimethylolpropane triacrylate 294.0

Charge 1 was added to a suitable reactor equipped with an overheadstirrer, thermocouple, condenser, and N₂ inlet. The charge was placedunder an N₂ blanket. Beginning at a temperature of 24° C., Charge 2 wasadded to the reactor over a period of 45 minutes. A mild exotherm wasobserved during the addition. At the completion of the charge, thetemperature of the reaction mixture was 26° C. The contents of thereactor were heated to 35° C. with an external heat source and held atthis temperature for 2 hours. Inspection of the infrared spectrum atthis time indicated consumption of the acrylate (absence of peaks at1621, 1635 cm⁻¹). The resulting material was found to have a measuredsolids content of (110° C., 1 hr) of 89.5 percent, a viscosity of C-D onthe Gardner-Holt scale, a density of 7.93 lb/gal, a total amine contentof 4.098 meq/g, and a M_(w) of 928 and a M_(n) of 692 as determined bygel permeation chromatography vs. a polystyrene standard.

Example D

An amine/epoxy adduct was prepared from the following ingredients:

Ingredient Wt in g Charge 1 Isophorone diamine 2044.8 Charge 2 CARDURAE10 P¹ 6000.0 ¹Glycidyl ether of neodecanoic acid, available from HexionSpecialty Chemicals, Inc.

Charge 1 was added to a suitable reactor equipped with an overheadstirrer, thermocouple, condenser, and N₂ inlet. The charge was placedunder an N₂ blanket and heat applied to the reactor. Beginning at atemperature of 62° C., Charge 2 was added to the reactor over a periodof 6.9 hours over a temperature range of 62 to 92° C. During the feed,the heating mantle was raised or lowered and cooling (water bath or airflow) applied to the reactor as required to control the reactiontemperature. At the completion of the addition, the temperature of thereaction mixture was 77° C. The reaction mixture was held at 80° C. for8.6 hours, then at 85° C. for 1.6 hours. At this time the epoxyequivalent weight was found to be 55556, and the reaction was judged tobe complete. The resulting material was found to have a measured solidscontent of (110° C., 1 hr) of 98.7 percent, a viscosity of Z10 on theGardner-Holt scale, a total amine content of 2.969 meq/g, a residualprimary amine content of 0.170 meq/g, a secondary amine content of 2.504meq/g, a tertiary amine content of 0.295 meq/g, a hydroxyl value of160.1, and a M_(w) of 657 and a M_(n) of 562 as determined by gelpermeation chromatography vs. a polystyrene standard.

Example E

An acrylate/aspartate amine curative was prepared from the followingingredients:

Ingredient Wt in g Charge 1 Isophorone diamine 170.4 2,6-di-tert-butylp-cresol 0.2 Charge 2 Diethyl maleate 168.8 Charge 3 2,6-di-tert-butylp-cresol 3.5 Charge 4 Butyl acrylate 125.4

Charge 1 was added to a suitable flask equipped with an overheadstirrer, thermocouple, condenser, and N₂ inlet. The charge was placedunder an N₂ blanket. Beginning at a temperature of 21° C., Charge 2 wasadded to the flask over a period of 45 minutes. An exotherm was observedduring the addition. At the completion of the charge, the temperature ofthe reaction mixture was 45° C. The reaction mixture was heated to atemperature of 50° C. with an external heat source and held at thistemperature for 3.25 hours. Inspection of the infrared spectrum of thereaction mixture indicated consumption of dibutyl maleate (disappearanceof peak at 1646 cm⁻¹). Charge 3 was added to the reactor, then Charge 4was added to the reaction mixture over 45 minutes; at the completion ofCharge 4 the reaction temperature was 50° C. The reaction mixture washeld at this temperature for 2.9 hours. Inspection of the infraredspectrum of the reaction mixture indicated the presence of unreactedacrylate (peaks at 1621, 1635 cm⁻¹). The temperature of the reactionmixture was raised to 70° C. and held for 4 hours. Inspection of theinfrared spectrum of the reaction mixture indicated the acrylate wasconsumed. The resulting material was found to have measured solidscontent (110° C., 1 hr) of 92.0 percent, a viscosity of C on theGardner-Holt scale, a density of 8.41 lb/gal, a total amine content of4.165 meq/g, a residual primary amine content of 0.026 meq/g, asecondary amine content of 4.139 meq/g, a tertiary amine content of0.000 meq/g, and a M_(w) of 489 and a M_(n) of 415 as determined by gelpermeation chromatography vs. a polystyrene standard.

Example F

An acrylate/aspartate amine curative was prepared from the followingingredients:

Ingredient Wt in g Charge 1 Isophorone diamine 2982.0 2,6-di-tert-butylp-cresol 3.5 Charge 2 Dibutyl maleate 1995.0 Charge 3 2,6-di-tert-butylp-cresol 3.5 Charge 4 Butyl acrylate 3270.4

Charge 1 was added to a suitable flask equipped with an overheadstirrer, thermocouple, condenser, and N₂ inlet. The charge was placedunder a N₂ blanket. Beginning at a temperature of 21° C., Charge 2 wasadded to the flask over a period of 5.75 hours. A mild exotherm wasobserved during the addition. A maximum temperature of 35° C. wasobserved during the addition of this charge. At the completion of thecharge, the temperature of the reaction mixture was 33° C. The reactionmixture was heated to a temperature of 35-37° C. with an external heatsource and held at this temperature for 3 hours. Inspection of theinfrared spectrum of the reaction mixture indicated consumption ofdibutyl maleate (disappearance of peak at 1646 cm⁻¹). Charge 3 was addedto the reactor, and the reaction mixture heated to 43° C. Charge 4 wasadded to the reaction mixture for 3.6 hours; a mild exotherm wasobserved. The temperature range of the reaction mixture over the courseof Charge 4 was between 43 and 50° C.; at the completion of Charge 4 thetemperature was 45° C. The temperature of the reaction mixture was thenraised to 50° C. and held for 3 hours. Inspection of the infraredspectrum of the reaction mixture indicated the presence of unreactedacrylate (peaks at 1621, 1635 cm⁻¹). The temperature of the reactionmixture was raised to 70° C. and held for 10.9 hours. Inspection of theinfrared spectrum of the reaction mixture indicated that the presencethe aforementioned peaks attributed to the acrylate could not bedistinguished from baseline noise; at this point the reaction was judgedto be complete. The resulting material was found to have measured solidscontent (110° C., 1 hr) of 98.9 percent, a viscosity of D on theGardner-Holt scale, a density of 8.17 lb/gal, a total amine content of4.21 meq/g, a residual primary amine content of 0.230 meq/g, a secondaryamine content of 3.985 meq/g, a tertiary amine content of 0.000 meq/g,and a M_(w) of 450 and a M_(n) of 406 as determined by gel permeationchromatography vs. a polystyrene standard.

Example G

An acrylate/aspartate amine curative was prepared from the followingingredients:

Ingredient Wt in g Charge 1 Isophorone diamine 383.4 2,6-di-tert-butylp-cresol 0.45 Charge 2 Diethyl maleate 193.5 Charge 3 2,6-di-tert-butylp-cresol 0.45 Charge 4 Ethyl acrylate 328.5

Charge 1 was added to a suitable flask equipped with an overheadstirrer, thermocouple, condenser, and N₂ inlet. The charge was placedunder a N₂ blanket. Beginning at a temperature of 23° C., Charge 2 wasadded to the flask over a period of 20 minutes. A mild exotherm wasobserved during the addition which was controlled by application of anice bath. A maximum temperature of 33° C. was observed during theaddition of this charge. At the completion of the charge, thetemperature of the reaction mixture was 28° C. The reaction mixture washeated to a temperature of 35-38° C. with an external heat source andheld at this temperature for 2.2 hours. Inspection of the infraredspectrum of the reaction mixture indicated the presence of diethylmaleate (peak at 1646 cm⁻¹). The temperature was raised to 50-51° C. andthe reaction mixture held for 7.6 hours. Inspection of the infraredspectrum of the reaction mixture indicated consumption of diethylmaleate. The temperature of the reaction mixture was taken to 41° C. andCharge 3 was added to the reactor. Charge 4 was added to the reactionmixture over 25 minutes; at the completion of Charge 4 the temperaturewas 39° C. The temperature of the reaction mixture was then raised to50° C. and held for 3 hours. Inspection of the infrared spectrum of thereaction mixture indicated the presence of unreacted acrylate (peaks at1621, 1635 cm⁻¹). The temperature of the reaction mixture was raised to70° C. and held for 7.5 hours, then raised to 80° C. and held for 3.75hours. Inspection of the infrared spectrum of the reaction mixtureindicated that the presence the aforementioned peaks attributed to theacrylate were not present; at this point the reaction was judged to becomplete. The resulting material was found to have measured solidscontent (110° C., 1 hr) of 95.5 percent, a viscosity of B on theGardner-Holt scale, a density of 8.34 lb/gal, a total amine content of5.096 meq/g, a residual primary amine content of 0.003 meq/g, asecondary amine content of 5.093 meq/g, a tertiary amine content of0.000 meq/g, and a M_(w) of 356 and a M_(n) of 321 as determined by gelpermeation chromatography vs. a polystyrene standard.

Example H

A partially aspartate functional amine was prepared from the followingingredients:

Ingredient Wt in g Charge 1 Isophorone diamine 596.4 2,6-di-tert-butylp-cresol 0.7 Charge 2 Dibutyl maleate 798.0Charge 1 was added to a suitable flask equipped with an overheadstirrer, thermocouple, condenser, and N₂ inlet. The charge was placedunder a N₂ blanket. Beginning at a temperature of 22° C., Charge 2 wasadded to the flask over a period of 2.7 hours. A mild exotherm wasobserved during the addition which was controlled by application of anice bath. A maximum temperature of 32° C. was observed during theaddition of this charge. At the completion of the charge, thetemperature of the reaction mixture was 31° C. The reaction mixture washeated to a temperature of 35° C. with an external heat source and heldat this temperature for 3.8 hours. Inspection of the infrared spectrumof the reaction mixture indicated the presence of dibutyl maleate (peakat 1646 cm⁻¹). The reaction mixture was then heated for an additional4.9 hours. Inspection of the infrared spectrum of the reaction mixtureat this point indicated consumption of dibutyl maleate. The resultingmaterial was found to have measured solids content (110° C., 1 hr) of89.0 percent, a viscosity of D on the Gardner-Holt scale, a density of8.18 lb/gal, a total amine content of 4.926 meq/g, a primary aminecontent of 2.541 meq/g, a secondary amine content of 2.385 meq/g, and atertiary amine content of 0.000 meq/g.

Example I

An acrylate terminal amine adduct was prepared from the followingingredients:

Ingredient Wt in g Charge 1 1,6-hexamethylene diacrylate 684.84-methoxyphenol 0.5 Charge 2 2,2′-dimethyl-4,4′-methylenebis 361.2cyclohexylamine

Charge 1 was added to a suitable flask equipped with an overheadstirrer, thermocouple, condenser, and air inlet. The charge was placedunder an air blanket and heated to 37° C. Charge 2 was added to the over40 minutes at this temperature. Immediately after Charge 2 was completea sample was taken inspection by attenuated total reflectance (ATR)infrared spectroscopy. Over the next 1.5 hours the temperature of thereaction mixture was gradually increased to 77° C. The reaction mixturewas again sampled at this point for ATR infrared spectroscopy. Thereaction mixture was held between 74-77° C. for 12.1 hours with periodicsampling for ATR infrared spectroscopy. The reaction was determined tobe complete when there was no further change in the peaks at 1621 and1635 cm⁻¹. The resulting material was found to have measured solidscontent (110° C., 1 hr) of 87.6 percent, a viscosity of Z1 on theGardner-Holt scale, a total amine content of 2.882 meq/g, a primaryamine content of 0.007 meq/g, a secondary amine content of 2.875 meq/g,a tertiary amine content of 0.000 meq/g, a M_(w) of 2070, a M_(n) of891, and M_(z) of 3079 as determined by gel permeation chromatographyvs. a polystyrene standard.

Example J

An oligomeric aspartate/acrylate amine curative was prepared from thefollowing ingredients:

Ingredient Wt in g Charge 1 Partially aspartate functional amine 246.3of Example H 2,6-di-tert-butyl p-cresol 0.4 Charge 2 Acrylate terminalamine adduct of Example I 207.5Charge 1 was added to a suitable flask equipped with an overheadstirrer, thermocouple, condenser, and air inlet. The charge was placedunder an air blanket and heated to 40° C. Charge 2 was added to thereaction mixture over 75 minutes between 40-41° C. The reactiontemperature was increased to 75° C. and held for 6.1 hours. Inspectionof the infrared spectrum of the reaction mixture indicated the presenceof unreacted acrylate (peaks at 1621, 1635 cm⁻¹). The temperature of thereaction mixture was raised to 85° C. and held for 4.8 hours. Inspectionof the infrared spectrum of the reaction mixture still indicated thepresence of acrylate. An additional 5.6 g of Charge 1 was added to thereaction mixture and reaction held another 4.8 hours. At this point, theinfrared spectrum of the mixture indicated that the acrylate had beenconsumed. The resulting material was found to have measured solidscontent (110° C., 1 hr) of 99.9 percent, a density of 8.52 lb/gal, aviscosity of Z6 on the Gardner-Holt scale, a total amine content of3.967 meq/g, a primary amine content of 0.021 meq/g, a secondary aminecontent of 3.855 meq/g, a tertiary amine content of 0.091 meq/g, a M_(w)of 2424, a M_(n) of 825, and a M_(z) of 3896 as determined by gelpermeation chromatography vs. a polystyrene standard.

Example K

An acrylate modified amine curative was prepared from the followingingredients:

Ingredient Wt in g Charge 1 JEFFAMINE D2000² 3490.5 2,6-di-tert-butylp-cresol 7.77 Dibutyltin dilaurate 19.4 Charge 2 Butyl acrylate 437.9²Difunctional polyoxyalkyleneamine of approximately 2000 molecularweight, available from Huntsman Corporation.

Charge 1 was added to a suitable flask equipped with an overheadstirrer, thermocouple, condenser, and air inlet. The charge was placedunder an air blanket. Beginning at a temperature of 22° C., Charge 2 wasadded to the over 18 minutes. No exotherm was observed. The reactiontemperature was increased to 70° C. and held for 2.9 hours. Inspectionof the infrared spectrum of the reaction mixture indicated the presenceof unreacted acrylate (peaks at 1621, 1635 cm⁻¹). The temperature of thereaction mixture was raised to 90° C. and held for 8.8 hours. At thispoint, the infrared spectrum of the mixture indicated that the acrylatehad been consumed. The resulting material was found to have measuredsolids content (110° C., 1 hr) of 95.4 percent, a viscosity of G- on theGardner-Holt scale, a total amine content of 0.884 meq/g, a primaryamine content of 0.155 meq/g, a secondary amine content of 0.702 meq/g,a tertiary amine content of 0.022 meq/g, a M_(w) of 2180, a M_(n) of769, and M_(z) of 2993 as determined by gel permeation chromatographyvs. a polystyrene standard.

Example 1

An isocyanate functional “A” side formula was prepared from thefollowing ingredients:

Ingredients % by wt TERATHANE 650³ 21.0 1,2-butanediol 1.2 Neopenylglycol 1.2 Isophorone diisocyanate 27.1 DESMODUR N3400⁴ 49.4³Polytetramethylene ether glycol, available from Invista. ⁴Aliphaticpolyisocyanate resin based on hexamethylene diisocyanate, available fromBayer Corporation.

Terathane 650, neopenyl glycol, 1,2-butanediol, and a catalytic amountof dibutyltin dilaurate (0.013% by wt of the three glycols) were chargedto a suitable reactor under nitrogen. Isophorone diisocyanate was addedto the reactor over 105 minutes at a temperature range of 36-37° C. Overa period of 50 minutes the temperature of the mixture was increased to52° C. Over a period of 60 minutes the temperature increased to amaximum of 125° C. After another 60 minutes the resulting prepolymerequivalent weight was found to be within specification. The resultingprepolymer was cooled to 71° C. and poured into 87.9% of the DesmodurN3400 and stirred for 30 minutes. The remaining Desmodur N3400 was addedto adjust to a final isocyanate equivalent weight of 264.9.

Examples 2-3

Pigment grinds were prepared according to the formulas in Table 1:

TABLE 1 Example Ingredient 2 (wt in parts) Example 3 (wt in parts)JEFFAMINE T3000⁵ 25.0 22.0 Amine/aspartate of 28.0 39.0 Example B VULCANXC72⁶ 1.2 1.2 BYK 9077⁷ 0.6 BENTONE 34⁸ 3.0 3.5 ⁵Polyoxyalkylenetriamineof approximately 3000 MW, available from Huntsman Corporation. ⁶Carbonblack pigment, available from Cabot Corporation. ⁷Dispersing agent,available from Byk-Chemie GmbH. ⁸Organoclay rheology additive, availablefrom Elementis Specialities, Inc.

In each example, the ingredients were combined and charged to a PremierMill HM 1.5 VSD Series SuperMill (SPX Corporation) with an 85 percentcharge of 1.0 mm Mill Mates Plus TZP grind medium (Zircoa, Inc.) andground at a mill speed of 2400 rpm. The grinds were judged to becomplete when the particle size was found to be 7.5 Hegman upon drawdownon a fineness of grind gauge.

Examples 4-5

Base mixes were prepared according to the formulas in Table 2:

TABLE 2 Ingredient Example 4 Example 5 Pigment grind of Example 2 1329.2Pigment grind of Example 3 3087.4 N-(3-triethoxysilylpropyl)- 0.58 1.204,5-dihydroimidazole N-(n-butyl)-3- 0.65 1.32aminopropyltrimethoxysilane Dibutyltin dilaurate 11.5 23.5 TINUVIN 328⁹0.58 1.2 TINUVIN 292¹⁰ 11.5 23.5 ⁹UV absorber, available from CibaSpeciality Chemicals Corporation. ¹⁰Hindered amine light stabilizer,available from Ciba Speciality Chemicals Corporation.

Examples 6-8

The following “B” side formulations were produced according to theformulas in Table 3:

TABLE 3 Example 6 Example 7 Example 8 Ingredient (3528-22-6) (3528-22-9)(3528-19-9) Base mix of 220.8 220.8 Example 4 Base mix of 253.7 Example5 JEFFAMINE T3000 3.8 10.6 JEFFLINK 754¹¹ 45.8 27.7 Amine/aspartate of13.1 7.5 Example B Amine/acrylate 93.8 50.6 57.0 curative of Example CAmine/epoxy 90.8 adduct of Example D Acrylate/aspartate 26.6 aminecurative of Example E ¹¹Aliphatic secondary amine, available fromHuntsman Corporation.

The B side formulations of Table 3 above and the A side formulation ofExample 1 were charged to separate canisters and heated to 140° F. in anoven for 1-3 hrs prior to spraying. Polyurea coating compositions wereproduced by mixing a 1:1 volume ratio of the A-side components to eachthe B-side components in a static mix tube applicator device availablefrom Cammda Corporation. The coating compositions were applied to coldrolled steel panels coated with an electrodeposition primer and an epoxyacid clearcoat (NDCT 5002A available from PPG Industries, Inc.). Tacktimes for the coatings were determined by periodically touching thepanel with a gloved hand as previously described and were judged to betack free when the glove no longer stuck to the coatings.

Hardness values were determined by charging the A and B side componentsinto a double-barreled syringe equipped with a static mix tube and aModel 415-0011-00 50 mL 1:1 manual dispenser (Cammda Corporation) andinjecting the components at a 1:1 ratio using a into a mold to form a“puck” of approximately 5 cm in diameter and 0.25 cm in thickness. Thehardness of the polyurea coating puck at ambient temperature wasmeasured on the Shore D scale with a Model 212 Pencil Style DigitalDurometer (Pacific Transducer Corp.) 1 day after application. The puckswere then placed in a 140° F. oven for 1 day and the Shore D hardness ofthe coating measured with the puck in the oven to prevent cooling. Thepucks were removed from the oven to ambient temperature and the hardnessmeasured again at ambient temperature after 1 day.

The ratio of equivalents of isocyanate to amine was calculated as being1.034 for the polyurea formulation comprising the B side component ofExample 6, 1.296 for the polyurea formulation comprising the B sidecomponent of Example 7, and 1.077 for the polyurea formulationcomprising the B side component of Example 8.

The following properties of the polyurea coatings were determined asshown in Table 4.

TABLE 4 Example 6 Example 7 Example 8 Tack free time (sec) 22 61 47Hardness (Shore D) 1 day* 56 52 50 after cure, ambient temperatureHardness (Shore D) after 1 day 23 28 22 at 140° F. Hardness (Shore D) 1day at 50 51 44 ambient temperature after 140° F. *Example 8 measured 2days after cure

Examples 9-11

Pigment grinds were prepared according to the formulas in Table 5.

TABLE 5 Wt in g Ingredient Example 9 Example 10 Example 11Acrylate/asparate amine 367.0 444.0 curative of Example F JEFFAMINED2000/butyl 168.0 acrylate adduct of Example K JEFFAMINE T3000 436.9CLEARLINK 1000¹² 406.2 JEFFLINK 754 339.1 DESMOPHEN NH 1420¹³ 120.0TINUVIN 292 13.5 12.0 13.0 VULCAN XC72 16.2 14.4 15.7 BENTONE 34 47.041.6 45.3 ¹²Secondary cycloaliphatic diamine, available from Dorf KetalChemicals, LLC. ¹³Asparatic ester amine, available from BayerCorporation.

In each example, the ingredients were combined and charged to a ModelM250 bead mill (Eiger Machinery, Inc.) with 188 mL Zirconox 1.0 mm beads(Jyoti Ceramic Industries Pvt. Ltd.) and ground at a mill speed of 3500rpm. The grinds were judged to be complete when the particle size wasfound to be 7.5 Hegman upon drawdown on a fineness of grind gauge.

Examples 12-15

The following “B side” formulations were produced as indicated Table 6:

TABLE 6 Wt in g Exam- Example Example Example Ingredients ple 12 13 1415 Pigment grind 62.77 62.77 composition of Example 2 Pigment grind100.01 composition of Example 3 Pigment grind 156.41 composition ofExample 4 Oligomeric 22.5 aspartate/acrylate amine curative of Example JAcrylate/aspartate amine 72.19 curative of Example G JEFFAMINE D200026.48 JEFFAMINE T3000 9.60 JEFFAMINE D2000/butyl 26.48 1.50 acrylateadduct of Example K Dipropylene 10 10 9.87 diamine/diethyl maleateadduct of Example A JEFFLINK 754 15.0 Dibutyltin dilaurate 0.75 0.751.13 1.8

The B side formulations of Table 6 above and the A side formulation ofExample 1 were charged to separate canisters and heated to 140° F. in anoven for 4-6 hrs prior to spraying. Polyurea coating compositions wereproduced by mixing a 1:1 volume ratio of the A-side components to eachthe B-side components in a static mix tube applicator device availablefrom Cammda Corporation. The coating compositions were applied to coldrolled steel panels coated with an electrodeposition primer and an epoxyacid clearcoat (APR 26241 available from ACT Laboratories, Inc.). Tacktimes for the coatings were determined by periodically touching thepanel with a gloved hand as previously described and were judged to betack free when the glove no longer stuck to the coatings.

Hardness values were determined by charging the A and B side componentsinto a double-barreled syringe equipped with a static mix tube and a“Pneumatic applicator” (PC Cox Limited) and injecting the components ata 1:1 ratio using a into a mold to form a round “puck” of approximately6 cm in diameter and 0.2 cm in thickness. The hardness of the polyureacoating puck at ambient temperature was measured on the Shore D scalewith a Model 212 Pencil Style Digital Durometer (Pacific TransducerCorp.) 1 day after application. The pucks were then placed in a 140° F.“hot room” for 1 day and the Shore D hardness of the coating measuredwith the puck in the hot room to prevent cooling. The pucks were removedfrom the hot room to ambient temperature and the hardness measured againat ambient temperature after 1 day.

The ratio of equivalents of isocyanate to amine was calculated as being1.059 for the polyurea formulation comprising the B side component ofExample 12, 1.072 for the polyurea formulation comprising the B sidecomponent of Example 13, 1.092 for the polyurea formulation comprisingthe B side component of Example 14, and 1.082 for the polyureaformulation comprising the B side component of Example 15.

The following properties of the polyurea coatings were determined:

TABLE 7 Exam- Example Example Example ple 12 13 14 15 Tack free time(sec) 28 31 44 15 Hardness (Shore D) 1 day 72 68 64 66 after cure,ambient temperature Hardness (Shore D) after 1 35 35 28 34 day at 140°F. Hardness (Shore D) 1 day 68 66 70 66 at ambient temperature after140° F.

Whereas particular embodiments of this invention have been describedabove for purposes of illustration, it will be evident to those skilledin the art that numerous variations of the details of the presentinvention may be made without departing from the invention as defined inthe appended claims

1. The triamine/aspartate reaction product resulting from a Michaeladdition reaction of a triamine with a dialkyl maleate and/or a dialkylfumarate, wherein the reaction product has a viscosity of less than 2000cPs, and wherein the triamine has the structure

wherein each n is the same or different and is any integer.
 2. Thereaction product of claim 1, wherein the triamine comprises dipropylenetriamine.
 3. The reaction product of claim 1, wherein the triaminecomprises bis(hexamethylene)triamine.
 4. The reaction product of claim1, wherein the dialkyl maleate comprises diethyl maleate.
 5. Thereaction product of claim 1, wherein the dialkyl maleate comprisesdibutyl maleate.
 6. The reaction product of claim 1, wherein thereaction product excludes cycloaliphatic amines.
 7. The reaction productof claim 1, wherein the ratio of the equivalents of amine:equivalents ofmaleate/fumarate is 3:2.